Composition of matter and method of producing



Patented Mar. 5, 1935 COMPOSITION -,OF MATTER AND METHOD OF PRODUCING Ernest G. Peterson, Wilmington, Del., assignor to Hercules Powder Company, Wilmington,

Del.

, a corporatiop ot Delaware No Drawing. Application March 14, 1932,

Serial No. 598,871

24 Claims- (Cl. 260-8) My invention relates to a synthetic resin and molecules. In other words, in the case of glycerol method of producing and more particularly rehaving three hydroxyl groups the three groups lates to a new form of synthetic resin and method will not be completely combined with terpinenefor its production.

My invention broadly involves a reaction prodmaleic anhydride.

On the other hand, where, for example, for the 5 uct of a polyhydric alcohol and terpinene-maleic production of a desired product glycerol and anhydride, the product being characterized by terpinene-maleic anhydride are reacted in the the fact that the polyhydric alcohol is only parpresence of a substance which itself will comtially combined with terpinene-maleic anhydride. bine with the glycerol, the product will involve In carrying out my invention the partial comglycerol molecules combined partially with ter- 10 bination of the polyhydric alcohol with terpinenepinene-maleic anhydride molecules and partially maleic anhydride may be effected in various with molecules of the other substance used. In ways with the production of products possessed other words, the hydroxylgroups of the glycerol of varying and widely differing characteristics. will be combined with terpinene-maleic anhy- Thus, the partial combination may be accomdride in part and in part with the other subplished by causing the reaction between a polystance used.

hydric alcoholfand terpinene-maleic anhydride to Thus, in accordance with my invention it will be stopped prior to complete combination. of the now be understood that the novel product contempolyhydric alcohol with terpinene-maleic anhyplated by me involves a polyhydric alcohol pardride or by partially combining the polyhydric altially combined with terpinene-maleic anhydride cohol with some substance other than terpineneand that the novel method embodying my invenmaleic anhydride.

tion involves more particularly effecting the par- In carrying out my invention the reaction betial combination of a polyhydric alcohol and tween a polyhydric alcohol and terpineneterpinene-maleic anhydride in the presence of a maleic anhydride may be stopped prior to comsubstance which will enable termination of the plete combination of the alcohol with terpinenereaction before complete combination without itmaleic anhydride by any desired manipulation, self entering into the reaction or which entering but preferably will be effected through carrying into the reaction will partly combine with the alout the reaction in the presence of some substance cohol, which substances I shall hereinafter refer which will operate to either cause the alcohol to to as modifying agents.

be less reactive and thus render its reaction with The synthetic resins embodying my invention terpinene-maleic anhydride readily terminable will difier widely in their physical characteristics prior to its complete combination therewith, or and in their adaptability for various uses dependwhich will itself react with the alcohol and with ing upon the particular polyhydric alcohol used which the alcohol will partially combine. Alterand the method followed in their production. natively, the polyhydric alcohol may be pretreat- Thus, they may be hard or soft bodies or may ed for its partial combination with some suitable be viscous liquids and will be adaptable for use substance and finally reacted with terpinenefor various purposes, as, for example, in substitumaleic anhydride for its partial combination tion forgumsor resins in lacquers, varnishes, and therewith, or, where the reaction of the alcohol the like. with terpinene-maleic anhydride is stopped be- The terpinene-maleic anhydride for the forfore complete combination of the alcohol with the mation of the synthetic resins embodying my inanhydride the product may be reacted with a vention may be readily produced by reacting substance which will satisfy the remaining realpha-terpinene with maleic acid or maleic anactive portion of the alcohol.

hydride by the application of heat, for example,

As generally illustrative of the carrying out of as disclosed in the application for United States my invention where, for example, the product Patent filed by Ernest G. Peterson and Edwin desired involves the reaction of glycerol'with R. Littman, Serial No. 496,560, filed November terpinene-maleic anhydride and the reaction'is 18, 1930.

carried out in the presence of.a substance en- For reaction with the terpinene-maleic anhyabling the reaction to be readily terminated, the dride I may use any suitable polyhydric alcohol. product will comprise glycerol molecules with as, for example, glycerol, polyglyceroil and a glywhich have combined terpinene-maleic anhydride col, as ethylene glycol, propylene glycol, diethylene molecules, to an extent, however, insumcient to glycol, or the like, etc., etc. I may also use subfully satisfy the reactive capacity of the glycerol stituted polyhydric alcohols, as, for example,

cohol as. used herein. The polyhydric alcohol may be in admixture with a monohydric alcohol, such as ethyl, methyl, butyl alcohols, etc., etc.

As the modifying agent I may use various substances, as, for example, an organic acid, a natural resin or resin acid, as rosin or abietic acid, manila copal, congo copal, etc., etc., a vegetable or animal oil, as linseed oil, China-wood oil, castor oil, fish oil, etc., etc., or the fatty acids derived therefrom, fatty acids, such as stearic acid, oleic acid, etc., etc., and dibasic acids, such as succinic, maleic acid, tartaric acid, etc., etc.

It will be understood that I contemplate the use of operable equivalents for the polyhydric alcohols mentioned and for the several modifying agents mentioned.

In proceeding in accordance with my invention for the production of a synthetic resin, for example, a mixture of about parts by weight of terpinene-maleic anhydride, '75 parts of rosin (acid number 180) and 46 parts of glycerol are heated together at a temperature of about 210 C. for about seven hours and the temperature then raised to about 250 C. and the heating continued for about three hours. The treatment may be carried out in any suitable form of apparatus. During the heating considerable foaming will be noted and it is, therefore, desirable, as indicated above, to heat for a period at the lower temperature and to raise the temperature only when the reaction is nearly completed.

The synthetic resin prepared as above described will comprise glycerol partially combined with terpinene-maleic anhydride and partially with abietic acid of the rosin, which, as will be understood, is capable of reacting with the glycerol and does react in the preparation of the resin preventing complete combination of the-glycerol with the terpinene-maleic anhydride.

The synthetic resin prepared as indicated will be found to be of a very light color, very clear and transparent, to have an acid number of about 16 and a softening point of about C. The synthetic resin will be found to be soluble in va rious known ester solvents and to be soluble in acetone, etc., etc. The synthetic resin will be found tobe only slightly soluble in alcohol and hydrocarbon solvents.

As a further illustration, for example, 330 parts by weight of rosin (A. N. 170) are dissolved in 234 parts of terpinene-maleic anhydride by heating, and 115 parts of glycerol are added. The mixture is gradually heated to a temperature of 270 C. and maintained at that temperature for approximately '7 hours. Agitation may be employed but is not absolutely essential since the evolution of water vapor serves to keep the mixture well stirred. The excess of glycerol is removed by applying a vacuum to the resin while in the heated condition. The product will comprise glycerol partially combined with terpinenemaleic anhydride and partially with abietic acid.

By the above procedure a variety of esters having various characteristics and adaptable for various purposes, as for use in varnishes, lacquers, japans, paints, as substitutes for hard rubber and various other plastic articles, films, etc., etc. may be prepared by varying the proportions of rosin and of terpinene-maleic anhydride used with resultant variation in the proportionate combination of abietic acid and of terpinenemaleic anhydride with the glycerol.

As a further illustration, for example, 1'17 parts by weight of'terpinene-maleic anhydride and parts rosin (A. N; are heated together at about 150 C. to form a homogeneous solution, and '7'! parts of ethylene glycol are then added. The mixture is heated at the boiling point of the solution, approximately 210 C.,- for about 8 hours. The excess glycol may be removed at the completion of the reaction by applying a vacuum. The product will involve ethylene glycol partially combined with terpinene-maleic anhydride and partially with abietic acid.

And as will be understood resins having various desirable characteristics and adaptable for various purposes may be prepared by the above indicated procedure with the use as the modifying agent of various acidic gums, as congo or manila copal, etc., etc., in place of rosin and the use of another polyhydric alcohol, as polyglycerol, ethylene glycol, etc. in place of glycerol. The various resins will, as has been indicated, involve a polyhydric alcohol partially combined with terpinenesmaleic anhydride and partially with the acid of the particular resin used in its preparation.

As a further illustration of the procedure for the preparation of synthetic resins in accordance with my invention using, for example, a vegetable oil or an acid derived therefrom as a modifying agent, for example, about 234 parts by weight of terpinene-maleic anhydride and 56 parts of, for example, raw linseed oil are heated together until a homogeneous solution is produced, then about 62 parts by weight of glycerol is added and the mixture heated to a temperature of about 200 C. until the evolution of water vapor has ceased, indicating completion of the reaction. Completion of the reaction will usually require about 9 to 10 hours where the heating is at 200 C., or the required period may be shortened somewhat by using a slightly higher temperature.

.The product produced as above described, using linseed oil, will comprise largely glycerol partially combined with terpinene-maleic anhydride and partially reactive or uncombined, that is to say, a portion of a hydroxyl group of the glycerol or one or more of the groups will be uncombined with terpinene-maleicanhydride though at the temperature used there may be some decomposition of the linseed oil resulting in the freeing of the fatty acid of the linseed oil which, insofar as. such may be freed may combine with the portion of the glycerol uncombined with the terpinene-maleic anhydride. The presence of the linseed oil, however, will operate to enable the reaction between the glycerol and the terpinene-maleic anhydride to be terminated prior to complete combination of the terpinenemaleic anhydride with the glycerol and hence the product will be characterized by the fact that the glycerol molecules are not completely combined with terpinene-maleic anhydride though the uncombined portions of the glycerol molecules may be in whole or in part combined with the fatty acid of linseed oil or may be in whole or in part reactive.

The synthetic resin produced will be found to be soluble in acetone, toluol and ester solvents generally, will be found to possess a high degree of flexibility, to be largely resistant to water, to satisfactorily harden at ordinary temperatures by the absorption of oxygen and to lend itself desirably for various uses such, for example, as in the preparation of varnishes, lacquers and enamels.

As a further illustration. for example, 1053 parts by weight of terpinene-maleic anhydride are heated with about 252 parts of castor oil until a homogeneous solution results, then about 166 parts by weight of glycerol are added and the mixture heated at 215-220 C. until the evolution oi. water vapor has ceased indicating completion of the reaction. The castor oil will operate in much the same manner as does linseed oil, namely, it will enable the reaction between the glycerol and the terpinene-maleic anhydride to be terminated before complete combination of the glycerol with terpinene-maleic anhydride and with such combination with the glycerol and the fatty acid of castor oil as may result from the freeing of the fatty acid through decomposition of the oil at the temperature used. The resultant resin will be found to be light yellow in color, very clear and very tough, to be soluble in acetone and in ester solvents, to soften at approximately C. and to be compatible with nitrocellulose, rendering it desirable for use in nitrocellulose lacquers though it will be found to have various other uses, as for example, in varnishes, etc.

As a further illustration, for example, 351 parts by weight of terpinene-maleic anhydride are dissolved in 284 parts raw linseed oil, the mixture heated to C. and 92 parts of glycerol added. This mixture is then heated for eight hours at a temperature of 220 C. The resin produced is a pale yellow viscous liquid.

The resin will involve glycerol partly combined with terpinene-maleic anhydride and partly uncombined or combined with the acid of linseed oil insofar as such may be freed through decomposition of linseed oil at the temperature used.

As has been indicated synthetic resins embodying my invention may be produced by the use of fatty acids derived from vegetable or animal oils. Thus, for example, for the preparation of a synthetic resin embodying my invention 234 parts by weight of terpinene-maleic anhydride are heated with 283 parts of the mixture of fatty acids produced by the saponification of linseed oil and technically known as linseed fatty acids to form a homogeneous solution. To the hot solution 92 parts of glycerol are added and the mixture is heated at a temperature of 220 C. for approximately 6 hours. The temperature is then raised to 250 C. for two hours. The reaction is carried out in a vessel of such shape and construction that air may be excluded from the reaction mixture, as it is necessary to prevent oxidation of the fatty acids. carbon dioxide or nitrogen gas may be passed into the vessel during the heating.

Where the resin is produced by reacting 'ter pinene-maleic anhydride and a polyhydric alcohol in the presence of a fatty acid derived from a vegetable or animal oil, the resin product will involve essentially the polyhydric alcohol partially combined with terpinene-maleic anhydride and partially combined with thefatty acid used.

As a further illustration, for example, 293 parts by weight of terpinene-maleic anhydride and 142 parts of the fatty acids obtained by the saponiflcation of China-wood oil are heated for a few minutes to form a homogeneous solution and then 92 parts of glycerol are added. This mixture is heated in a closed vessel at a temperature of 215-220 C. for 5 to 6 hours in an inert atmosphere. The resin resulting is a transparent, light yellow solid. The resin will comprise essentially glycerol partially combined with ter- For example,

pinene-maelic anhydride and partially combined with the faty acid of China-wood oil.

In proceeding with the use of fatty acids the addition of a small amount of rosin in the preparation of these resins facilitates the reaction appreciably and prevents the formation of insoluble gels in many cases. Where the reaction is carried on in the presence of rosin as well as of a fatty acid, the resin product will involve the polyhydric alcohol partially combined with terpinene-maleic anhydride, with the fatty acid and with abietic acid.

As a further illustration, for example, 234 parts by weight of terpinene-maleic anhydride,

parts rosin (A. N. and 146 parts of the fatty acids derived from linseed oil are heated together at about 150 C. until a homogeneous mixture results and 92 parts of glycerol are then added. The mixture is heated at a temperature of 220 C. until the evolution of water vapor ceases, usually from 8 to 10 hours. The reaction mixture is protected from the air as described above. The product will involve glycerol partially combined with terpinene-maleic anhydride and partially with the fatty acid derived from linseed oil, and with abietic acid.

The resins produced as above from unsaturated fatty acids may be further heated with a drying oil such as China-wood oil to give an improved composition. For example, the resin as described, produced with the fatty acids obtained by saponiflcation of China-wood oil. may be heated with 50% of its weight of China-wood oil to give an improved composition having excellent water resistance.

As a further illustration, with the use, for example, of a dibasic acid, for example, 92 parts of glycerol are heated with 211 parts of terpinenemaleic anhydride and 71 parts of, for example, succinic acid at a temperature of ISO-200 C. for about 15 hours. Completion of the reaction may be noted by the fact that a cooled sample is not sticky. The resin produced will involve glycerol partially combined with terpinene-maleic anhydride and partially combined with succinic acid. The resin product may be improved for various uses by further heating, as for example, by heating at a temperature of about 100 C. for a period of 24 hours and heating at a higher temperature, say 150-200 C. for a period of say 15-24 hours.

It will be understood that the synthetic resins in accordance with my invention may be prepared by various procedures differing from those described above by way of illustration, that is to say various proportions of terpinene-maleic anhydride, of polyhydric alcohol and modifier may be i used as well as various temperatures and times of treatment, depending upon the substances used. As has been indicated, any suitable form of apparatus may be used and the procedure may be carried out under various pressure conditions as may be desirable, depending upon the substances reacted.

It will also be understood that if desirable the reaction may be promoted through the use of catalysts, as for' example, basic materials, such as calcium oxide or zinc oxide, or the like.

It will be clearly understood that I contemplate the production of the synthetic resins in accordance with my invention by the use of terpinenemaleic anhydride and of any suitable polyhydric alcohol including those specifically mentioned and operable equivalents therefor and with the use of any suitable modifying agent including those specifically mentioned and mixtures thereof and operable equivalents therefor.

It will be appreciated that the synthetic resin in accordance with my invention will involve essentially a polyhydric alcohol partially combined with 'tei'pinene-maleic anhydride and. partially reactive or partially combined with some othersubstance, the partial combination with a substance other than terpinene-maleic anhydride being accomplished simultaneously with the partial combination with terpinene-maleic anhydride or being effected prior to or subsequent to such combination.

In the preparation of the synthetic resin any suitable form of apparatus may be used and it will be understood that in place of linseed oil any drying oil, semi-drying oil or non-drying oil, as perilla oil, soya bean oil, China-wood oil, fish oil, castor oil, etc., or the corresponding fatty acids may be used in place of linseed oil as the modifying agent.

It will be understood that where in the claims appended hereto the term polyhydric alcohol is used such is intended to embrace and include substituted polyhydric alcohols as equivalents within the scope of this invention.

This application is filed as a continuation, in part, of the application for United States Letters Patent for improvement in composition of matter and method of producing filed by me April 24, 1931, Serial Number 532,683.

I have not specifically claimed herein my invention as it relates to reactions effected without the use of a substance which will enter into and modify the reaction by combining with the polyhydric alcohol, nor the products thereby produced, since such form the subject matter of and are claimed in my copending application, Serial No. 736,686, filed July 24, 1934.

What I claim and desire to protect Patent is:

1. A synthetic resin comprising a reaction product of a polyhydric alcohol, terpinene-maleic anhydride and a fatty acid.

2. A synthetic resin comprising a reaction product of a polyhydric alcohol selected from the group consisting'of glycerol and aliphatic glycols, terpinene-maleic anhydride and a fatty acid.

3. A synthetic resin comprising a reaction product of a polyhydric alcohol, terpinene-maleic anhydride and a linseed oil fatty acid.

4. A synthetic resin comprising a reaction product of a polyhydric alcohol selected from the group consisting of glycerol and aliphatic glycols, terpinene-maleic anhydride and a-linseed oil fatty acid.

5. The method of producing a synthetic resin which includes combining a polyhydric alcohol, terpinene-maleic anhydride and a fatty acid.

6. A synthetic resin comprising a reaction product of a polyhydric alcohol, terpinene-maleic anhydride and an organic carboxylic acid.

'7. A synthetic resin comprising a reaction product of a polyhydric alcohol, terpinene-maleic anhydride and a resin acid.

8. A synthetic resin comprising a reaction product of a polyhydric alcohol, terpineneby Letters maleic anhydride and abietic acid.

9. A synthetic rresin comprising a reaction product of a polyhydric alcohol, terpinenemaleic anhydride and a dibasic organic carboxylic acid.

10. A synthetic resin comprising a reaction product of a polyhydric alcohol, terpinene-maleic anhydride and succinic acid.

11. A synthetic resin comprising a reaction product of a polyhydric alcohol selected from the group consisting of glycerol and aliphatic glycols, terpinene-maleic anhydride and an organic carboxylic acid.

12. A synthetic resin comprising a reaction I product of a polyhydric alcohol selected from the group consisting of glycerol and aliphatic glycols,

-terpinene-maleic anhydride and a resin acid.

\ 13. A synthetic resin comprising a reaction product of a polyhydric alcohol selected from the group consisting of glycerol andaliphatic glycols, terpinene-maleic anhydride and abietic acid.

14. A synthetic resin comprising a reaction product of a polyhydric alcohol selected from the group consisting of glycerol and aliphatic glycols, terpinene-rnaleic anhydride and a dibasic organic carboxylic acid.

15. A synthetic resin comprising. a reaction product of a polyhydric alcohol selected from the group consisting of glycerol and aliphatic glycols, terpinene-maleic anhydride and succinic acid. 16. The method of producing a synthetic resin which includes combining a polyhydric alcohol, terpinene-maleic anhydride and an organic carboxylic acid.

17. The method of producing a synthetic resin which includes combining a polyhydric alcohol, terpinene-maleic anhydride and a resin acid.

18. The method of producing a synthetic resin which includes combining a polyhydric alcohol, terpinene-maleic anhydride and a dibasic organic carboxylic acid.

, 19. A coating composition comprising a reaction product of a polyhydric alcohol, terpinenemaleic anhydride and an organic carboxylic acid, and a solvent.

20. A coating composition comprising a reaction product ofa polyhydric alcohol, terpinenemaleic anhydride and an organic carboxylic acid, a lacquer ingredient and a solvent.

21. A coating composition comprising a reaction product of a polyhydric alcohol, terpinenemaleic anhydride and an organic carboxylic acid,

a varnish ingredient and a solvent.

22. A synthetic resin comprising a reaction product of a polyhydric alcohol, terpinene-maleic anhydride, a resin acid and a linseed oil fatty acid.

23. A synthetic resin comprising a reaction product-of a polyhydric alcohol selected from the group consisting of glycerol and aliphatic glycols, terpinene-maleic anhydride, abietic acid and a linseed oil fatty acid.

24. The method of producing a synthetic resin which includes combining a polyhydric alcohol, terpinene-maleic anhydride and a fatty acid in an inert atmosphere.

ERNEST G. PETERSON. 

